Metalloaluminophosphate molecular sieves, their synthesis and use

ABSTRACT

A process for manufacturing a metalloaluminophosphate molecular sieve, the process comprising the steps of: (a) combining at least one silicon source, at least one metal source, at least one structure-directing-agent (R), at least one phosphorus source, and at least one aluminum source to form a mixture having a molar composition according to formula:
 
(n)Si:Al 2 :(m)P:(x)R:(y)H 2 O:(z)M
 
wherein n is in the range of from about 0.005 to about 0.6, m is in the range of from about 1.2 to about 2.4, x is in the range of from about 0.5 to about 2, y is in the range of from about 10 to about 60, and z is in the range of from about 0.001 to 1; and (b) submitting the mixture to crystallization conditions to form the metalloaluminophosphate molecular sieve, wherein the metalloaluminophosphate molecular sieve has an X-ray diffraction pattern having a FWHM greater than 0.10 degree (2θ) and an AEI/CHA framework type ratio of from about 0/100 to about 40/60 as determined by DIFFaX analysis.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Provisional application filed onNov. 2, 2005, U.S. Ser. No. 60/732,830.

FIELD OF THE INVENTION

This invention relates to a process for manufacturingmetalloaluminophosphate molecular sieves, a metalloaluminophosphatemolecular sieve composition, and their use in a process for making anolefin product by contacting these metalloaluminophosphate molecularsieves with an oxygenate feedstock.

BACKGROUND OF THE INVENTION

Metalloaluminophosphate (MeAPO) molecular sieves contain lattice metalin tetrahedral coordination with oxygen atoms in a three-dimensionalmicroporous crystal framework structure of [SiO₂], [AlO₂], and [PO₂]corner sharing tetrahedral units. The [PO₂] tetrahedral units areprovided by a variety of compositions including phosphoric acid, organicphosphates such as triethyl phosphate, and aluminophosphates. The [AlO₂]tetrahedral units are provided by a variety of compositions includingaluminum alkoxides such as aluminum isopropoxide, aluminum phosphates,aluminum hydroxide, sodium aluminate, and pseudoboehmite. The [SiO₂]tetrahedral units are provided by a variety of compositions includingsilica sols and silicon alkoxides such as tetraethylorthosilicate andfumed silica. The metal tetrahedral units are provided by a variety ofcompositions including Mg, Mn, Zn, and Co compounds.

SAPO-34 and SAPO-18 have been reported as suitable catalysts for lightolefin production from methanol. SAPO-34 belongs to the family ofmolecular sieves having the structure type of the zeolitic mineralchabazite (CHA). The preparation and characterization of SAPO-34 hasbeen reported in several publications, including U.S. Pat. No.4,440,871; J. Chen et al. in “Studies in Surface Science and Catalysis”,Vol. 84, pp. 1731-1738; U.S. Pat. No. 5,279,810; J. Chen et al. in“Journal of Physical Chemistry”, Vol. 98, pp. 10216-10224, 1994; J. Chenet al. in “Catalysis Letters”, Vol. 28, pp. 241-248, 1994; A. M. Prakashet al. in “Journal of the Chemical Society, Faraday Transactions,” Vol.90(15), pp. 2291-2296, 1994; Yan Xu et al. in “Journal of the ChemicalSociety, Faraday Transactions” vol. 86(2), pp. 425-429, 1990, all ofwhich are herein fully incorporated by reference.

U.S. Pat. No. 6,334,994, incorporated herein by reference, discloses asilicoaluminophosphate molecular sieve, referred to as RUW-19, which issaid to be an AEI/CHA mixed phase composition. In particular, RUW-19 isreported as having peaks characteristic of both CHA and AEI frameworktype molecular sieves, except that the broad feature centered at about16.9 (2θ) in RUW-19 replaces the pair of reflections centered at about17.0 (2θ) in AEI materials and RUW-19 does not have the reflectionsassociated with CHA materials centered at 2θ values of 17.8 and 24.8.DIFFaX analysis of the X-ray diffraction pattern of RUW-19 as producedin Examples 1, 2, and 3 of U.S. Pat. No. 6,334,994 indicates that thesematerials are characterized by single intergrown phases of AEI and CHAframework type molecular sieves with AEI/CHA ratios of about 60/40,65/35, and 70/30, respectively. Throughout this description, the XRDreflection values are referred to as (2θ), which is synonymous to theexpression “degrees 2θ.”

U.S. Pat. No. 6,812,372, incorporated herein by reference, discloses asilicoaluminophosphate molecular sieve, comprising at least oneintergrown phase of molecular sieves having AEI and CHA framework types,wherein said intergrown phase has an AEI/CHA ratio of from about 5/95 to40/60 as determined by DIFFaX analysis, using the powder X-raydiffraction pattern of a calcined sample of said metalloaluminophosphatemolecular sieve.

U.S. patent application Ser. Nos. 10/092,792 and 10/995,870 disclose asilicoaluminophosphate molecular sieve comprising at least oneintergrown phase of molecular sieves having AEI and CHA framework types,wherein the intergrown phase has an AEI/CHA ratio of from about 5/95 to40/60 as determined by DIFFaX analysis, using the powder X-raydiffraction pattern of a calcined sample of the metalloaluminophosphatemolecular sieve. It also relates to methods for its preparation and toits use in the catalytic conversion of methanol to olefins.

U.S. patent application Ser. No. 10/425,587 discloses methods andcompositions of synthesis mixtures for the synthesis ofaluminophosphates and silicoaluminophosphate molecular sieves, whichenable the control and adjustment of the crystal particle size ofaluminophosphates and silicoaluminophosphate molecular sieves. Thesynthesis mixture compositions used have two or more organic templatespresent at a molar ratio of total template to aluminum of ≦1.25; such asynthesis mixture is susceptible to control of product particle sizethrough variation in the amount of seeds used in the synthesis.

U.S. Pat. No. 4,567,029 discloses a crystalline microporous metalaluminophosphate compositions containing as lattice constituents inaddition to AlO₂ and PO₂ structure units, one or a mixture of two ormore of the metals Mg, Mn, Co, and Zn in tetrahedral coordination withoxygen atoms (MAPO).

U.S. Pat. No. 5,912,393 discloses a catalyst for converting methanol tolight olefins. The catalyst is a metalloaluminophosphate molecular sievehaving the empirical formula (EL_(x)Al_(y)P_(z))O₂ where EL is a metalsuch as silicon or magnesium and x, y, and z are the mole fractions ofEL, Al, and P respectively. The molecular sieve has a crystal morphologyin which the average smallest crystal dimension is at least 0.1 microns.Use of this catalyst gives a product with a larger amount of ethyleneversus propylene.

EP Patent Application No. 1,142,833 discloses a class of microporousmetalloaluminophosphate molecular sieves (MeAPSOs) and the method oftheir fast preparation. These molecular sieves can be represented by theempirical formula on an anhydrous basis: mR.(M_(q)Si_(x)Al_(y)P_(z))O₂,wherein “R” represents the templating agent presented in theintracrystalline pore system; “m” is the molar amount of “R” per mole of(M_(q)Si_(x)Al_(y)P_(z))O₂ and has a value from 0.01 to 8.00; “M”represents at least one metal element; “q”, “x”, “y”, and “z” representthe molar fractions of metal, silicon, aluminum, and phosphorusrespectively, whose variations are q=0−0.98, x=0−0.98, y=0.01−0.60,z=0.01−0.60, and q+x+y+z=1. The crystallization time of the synthesis is0.5-12 hours, which is defined as the method of fast preparation.

SUMMARY OF THE INVENTION

The present invention is related to a metalloaluminophosphate molecularsieve having an X-ray diffraction pattern having a FWHM greater than0.10 degree (2θ) and an AEI/CHA framework type ratio of from about 0/100to about 40/60 as determined by DIFFaX analysis and a process formanufacturing and using such metalloaluminophosphate molecular sieves.

In one embodiment, the present invention relates to a process formanufacturing a metalloaluminophosphate molecular sieve, the processcomprising the steps of:

-   (a) combining at least one silicon source, at least one metal    source, at least one structure-directing-agent (R), at least one    phosphorus source, and at least one aluminum source to form a    mixture having a molar composition according to formula (I):    (n)Si:Al₂:(m)P:(x)R:(y)H₂O:(z)M  (I)    -   wherein n is in the range of from about 0.005 to about 0.6, m is        in the range of from about 1.2 to about 2.4, x is in the range        of from about 0.5 to about 2, y is in the range of from about 10        to about 60, and z is in the range of from about 0.001 to 1; and-   (b) submitting the mixture to crystallization conditions to form the    metalloaluminophosphate molecular sieve,    -   wherein the metalloaluminophosphate molecular sieve has an X-ray        diffraction pattern having a FWHM greater than 0.10 degree (2θ)        and an AEI/CHA framework type ratio of from about 0/100 to about        40/60 as determined by DIFFaX analysis.

In another embodiment, this invention relates to ametalloaluminophosphate molecular sieve manufactured in according to theprocess described in the paragraph above.

In yet another embodiment, this invention relates to a process for theconversion of an oxygenate to olefins, the process comprising the stepsof:

-   (i) contacting the oxygenate under catalytic conversion conditions    with the metalloaluminophosphate molecular sieve made in according    to the process described above in steps (a) and (b); and-   (ii) withdrawing the olefins from the reactor.

In yet another embodiment, this invention relates to ametalloaluminophosphate molecular sieve, the metalloaluminophosphatemolecular sieve having a composition represented by empirical formula(II) on an anhydrous basis as:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (II)wherein p is in the range of from about 0.001 to about 0.5, q is in therange of from about 0.001 to about 0.25, r is in the range of from about0.01 to about 0.15, s is in the range of from about 0.01 to about 0.6, tis in the range of from about 0.001 to 0.6, and the sum of q, r, s, andt is 1, wherein the metalloaluminophosphate molecular sieve has an X-raydiffraction pattern having a FWHM greater than 0.10 degree (2θ) and anAEI/CHA framework type ratio of from about 0/100 to about 40/60 asdetermined by DIFFaX analysis.

In yet another embodiment, this invention relates to a process for theconversion of an oxygenate to olefins, the process comprising the stepsof:

-   (i) contacting the oxygenate under catalytic conversion conditions    with the metalloaluminophosphate molecular sieve having a    composition represented by the empirical formula as described above;    and-   (ii) withdrawing the olefins from the reactor.

For each of these embodiments, the metalloaluminophosphate molecularsieve has a shredded crystal morphology by SEM.

DESCRIPTION OF THE FIGURES

FIG. 1 is a SEM image of a shredded morphology metalloaluminophosphatemolecular sieve of Example 4.

FIG. 2 is an XRD pattern of the metalloaluminophosphate molecular sieveof Example 1.

FIG. 3 is an XRD pattern of the metalloaluminophosphate molecular sieveof Example 2.

FIG. 4 is an XRD pattern of the metalloaluminophosphate molecular sieveof Example 3.

FIG. 5 is an XRD pattern of the metalloaluminophosphate molecular sieveof Example 4.

FIG. 6 is an XRD pattern of the metalloaluminophosphate molecular sieveof Example 5.

DETAILED DESCRIPTION OF THE INVENTION

Metalloaluminophosphate molecular sieves are generally well known tothose skilled in the art, for example, U.S. Pat. No. 4,567,029 (MeAPOwhere Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871 (SAPO), EPApplication No. E.P. 0,159,624 (ELAPSO where El is As, Be, B, Cr, Co,Ga, Ge, Fe, Li, Mg, Mn, Ti, or Zn), U.S. Pat. No. 4,554,143 (FeAPO);U.S. Pat. Nos. 4,822,478; 4,683,217; 4,744,885 (FeAPSO); EP 0,158,975;and U.S. Pat. No. 4,935,216 (ZnAPSO); EP-A-0 161 489 (CoAPSO); EP0,158,976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti, or Zn); U.S. Pat. No.4,310,440 (AlPO4); Patent Application No. EP 0,158,350 (SENAPSO); U.S.Pat. No. 4,973,460 (LiAPSO); U.S. Pat. No. 4,789,535 (LiAPO); U.S. Pat.No. 4,992,250 (GeAPSO); U.S. Pat. No. 4,888,167 (GeAPO); U.S. Pat. No.5,057,295 (BAPSO); U.S. Pat. No. 4,738,837 (CrAPSO); U.S. Pat. Nos.4,759,919, and 4,851,106 (CrAPO); U.S. Pat. Nos. 4,758,419; 4,882,038;5,434,326; and 5,478,787 (MgAPSO); U.S. Pat. No. 4,554,143 (FeAPO); U.S.Pat. No. 4,894,213 (AsAPSO); U.S. Pat. No. 4,913,888 (AsAPO); U.S. Pat.Nos. 4,686,092; 4,846,956; and 4,793,833 (MnAPSO); U.S. Pat. Nos.5,345,011 and 6,156,931 (MnAPO); U.S. Pat. No. 4,737,353 (BeAPSO); U.S.Pat. No. 4,940,570 (BeAPO); U.S. Pat. Nos. 4,801,309; 4,684,617; and4,880,520 (TiAPSO); U.S. Pat. Nos. 4,500,651; 4,551,236; and 4,605,492(TiAPO); U.S. Pat. Nos. 4,824,554; 4,744,970 (CoAPSO); U.S. Pat. No.4,735,806 (GaAPSO); Patent Application No. EP 0,293,937 (QAPSO, where Qis framework oxide unit [QO₂]); as well as U.S. Pat. Nos. 4,567,029;4,686,093; 4,781,814; 4,793,984; 4,801,364; 4,853,197; 4,917,876;4,952,384; 4,956,164; 4,956,165; 4,973,785; 5,241,093; 5,493,066; and5,675,050; all of which are herein fully incorporated by reference.

Other metalloaluminophosphate molecular sieves include those describedin patent No. EP 0,888,187 (microporous crystallinemetalloaluminophosphates (UIO-6)), U.S. Pat. No. 6,004,898 (molecularsieve and an alkaline earth metal), U.S. patent application Ser. No.09/511,943, filed Feb. 24, 2000 (integrated hydrocarbon co-catalyst),PCT WO 01/64340 published Sep. 7, 2001 (thorium containing molecularsieve), and R. Szostak, Handbook of Molecular Sieves, Van NostrandReinhold, New York, N.Y. (1992), which are all herein fully incorporatedby reference.

The preferred molecular sieves are SAPO molecular sieves and metalsubstituted SAPO molecular sieves. In one embodiment, the metal is analkali metal of Group IA of the Periodic Table of Elements, an alkalineearth metal of Group IIA of the Periodic Table of Elements, a rare earthmetal of Group IIIB, including the Lanthanides: lanthanum, cerium,praseodymium, neodymium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, and lutetium; andscandium or yttrium of the Periodic Table of Elements, a transitionmetal of Groups IVB, VB, VIB, VIIB, VIIIB, and IB of the Periodic Tableof Elements, or mixtures of any of these metal species. In one preferredembodiment, the metal is selected from the group consisting of Co, Cr,Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, and Zr, and mixtures thereof. Ina more preferred embodiment, the metal comprises at least one of Mg, Zn,and mixtures thereof.

In one embodiment, the metalloaluminophosphate molecular sieve has acomposition represented by empirical formula (II) on an anhydrous basisas:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (II)wherein R represents at least one templating agent, preferably anorganic templating agent; p is the number of moles of R per mole of(M_(q)Si_(r)Al_(s)P_(t))O₂ and p has a value from about 0.001 to about0.5, preferably 0.001 to 0.4, more preferably from 0.001 to 0.3, mostpreferably from 0 to 0.2; q, r, s, and t represent the mole fraction ofM, Si, Al, and P as tetrahedral oxides, where M is a metal selected fromone of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB andLanthanide's of the Periodic Table of Elements. Preferably M is selectedfrom one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni,Sn, Ti, Zn, and Zr. In an embodiment, p is greater than or equal to 0.2and q, r, s, and t are greater than or equal to 0.001. In anotherembodiment, p is greater than 0.1 to about 1, q is greater than 0.001 toabout 0.25, r is greater than 0.01 to about 0.15, s is in the range offrom 0.4 to 0.5, and t is in the range of from 0.25 to 0.5. Morepreferably p is from 0.15 to 0.7, q is from 0.001 to 0.1, r is from 0.01to 0.1, s is from 0.4 to 0.5, and t is from 0.3 to 0.5.

In another embodiment, the metalloaluminophosphate molecular sieve is amixture of AEI and/or CHA framework type molecular sieves which has anAEI/CHA framework type ratio of from about 0/100 to about 40/60 asdetermined by DIFFaX analysis. In one embodiment, themetalloaluminophosphate molecular sieve is substantially free of non-CHAframework type molecular sieve. The term “substantially free”, as usedherein, means less than 5 wt. %, preferably less than 1 wt. %, even morepreferably less than 0.5 wt. % of the metalloaluminophosphate molecularsieve having non-CHA framework type molecular sieve.

As used herein, the term “mixture” is synonymous with combination and isconsidered a composition of matter having two or more components invarying proportions, regardless of their physical state. In reference tomolecular sieve structure, it encompasses physical mixtures, as well asintergrowths of at least two different molecular sieve structures; suchas, for example those described in PCT Publication No. WO 98/15496 andco-pending U.S. Ser. No. 09/924,016, filed Aug. 7, 2001. In oneembodiment, the molecular sieve is an intergrowth material having two ormore distinct phases of crystalline structures within one molecularsieve composition. In another embodiment, the molecular sieve comprisesat least one intergrown phase of AEI and CHA framework types. Forexample, SAPO-18, ALPO-18, and RUW-18 have an AEI framework-type, andSAPO-34 has a CHA framework-type. In a further embodiment the molecularsieve comprises a mixture of intergrown material, and non-intergrownmaterial.

Intergrown molecular sieve phases are disordered planar intergrowths ofmolecular sieve frameworks. These are generally described in the“Catalog of Disordered Zeolite Structures”, 2000 Edition, published bythe Structure Commission of the International Zeolite Association and tothe “Collection of Simulated XRD Powder Patterns for Zeolites”, M. M. J.Treacy and J. B. Higgins, 2001 Edition, published on behalf of theStructure Commission of the International Zeolite Association for adetailed explanation on intergrown molecular sieve phases.

Regular crystalline solids are periodically ordered in three dimensions.Structurally disordered structures show periodic ordering in dimensionsless than three, i.e., in two, one, or zero dimensions. This phenomenonis called stacking disorder of structurally invariant Periodic BuildingUnits. Crystal structures built from Periodic Building Units are calledend-member structures if periodic ordering is achieved in all threedimensions. Disordered structures are those where the stacking sequenceof the Periodic Building Units deviates from periodic ordering up tostatistic stacking sequences.

The molecular sieves of the present invention are disordered planarintergrowths of end-member structures AEI and CHA. We refer to A. Simmenet al. in Zeolites (1991), Vol. 11, pp. 654-661, describing thestructure of molecular sieves with AEI and CHA framework types. For AEIand CHA, the Periodic Building Unit is a double six-ring layer. Thereare two types of layers “a” and “b”, which are identical except “b” isthe mirror image of “a” (180° rotation about the plane normal or mirroroperation perpendicular to the plane normal). When layers of the sametype stack on top of one another, i.e., aaa or bbb, the framework typeCHA is generated. When layers “a” and “b” alternate, i.e., abab, theframework type AEI is generated. The molecular sieves of the presentinvention are made of stackings of layers “a” and “b” which containregions of CHA framework type and regions of AEI framework type. Eachchange of CHA to AEI framework type is a stacking disorder or planarfault.

Preferably, the molecular sieves of the invention possess an AEI/CHAratio of from about 7/93 to 38/62, more preferably from about 8/92 to35/65, even more preferably from about 9/91 to 33/67, most preferablyfrom about 10/90 to 30/70 as determined by DIFFaX analysis, using thepowder X-ray diffraction (XRD) pattern of a calcined sample of themetalloaluminophosphate molecular sieve.

The X-ray diffraction data referred to herein are collected with aSCINTAG X2 X-Ray Powder Diffractometer (Scintag Inc., USA), using copperK-alpha radiation. The diffraction data are recorded by step-scanning at0.02 degrees of two-theta (2θ), where theta is the Bragg angle, and acounting time of 1 second for each step. Prior to recording of eachexperimental X-ray diffraction pattern, the sample must be in theanhydrous state and free of any template used in its synthesis, sincethe simulated patterns are calculated using only framework atoms, notwater or template.

While not wishing to be bound by theory, we believe that the combinationof addition of metal, silicon source, and the preparation procedurecontribute to a large extent to the small particle size, which ischaracterized by the FWHM and SEM.

Given the sensitivity of metalloaluminophosphate materials to water atrecording temperatures, the molecular sieve samples are calcined afterpreparation and kept moisture-free according to the following procedure.About 2 grams of each molecular sieve sample are heated in an oven fromroom temperature under a flow of nitrogen at a rate of 3° C./minute to200° C. and, while retaining the nitrogen flow, the sample is held at200° C. for 30 minutes and the temperature of the oven is then raised ata rate of 2° C./minute to 650° C. The sample is then retained at 650° C.for 8 hours, the first 5 hours being under nitrogen and the final 3hours being under air. The oven is then cooled to 200° C. at 30°C./minute and, when the XRD pattern is to be recorded, the sample istransferred from the oven directly to a sample holder and covered withMylar foil to prevent rehydration. It is also possible after cool-downto room temperature, to do a fast recording of the XRD patternimmediately after removal of the Mylar foil (e.g., by using a total scantime of less than 5 minutes).

The full-width-half-maximum (FWHM) is measured by measuring the fillwidth at the half maximum intensity after background subtraction of anyXRD peak in unit of degree (2θ). In one embodiment, the molecular sieveof this invention has an X-ray diffraction pattern having a FWHM greaterthan 0.1 degree (2θ), preferably greater than 0.15 degree (2θ), and,optionally, greater than 0.4 degree (2θ). In another embodiment, themolecular sieve of this invention has an X-ray diffraction patternhaving a FWHM greater than 0.1 degree (2θ) for the peak at 20.6 degree(2θ), preferably greater than 0.15 degree (2θ) for the peak at 20.6degree (2θ), and optionally greater than 0.4 degree (2θ) for the peak at20.6 degree (2θ).

In the case of crystals with planar faults, interpretation of XRDdiffraction patterns requires an ability to simulate the effects ofstacking disorder. DIFFaX is a computer program based on a mathematicalmodel for calculating intensities from crystals containing planar faults(see M. M. J. Tracey et al., Proceedings of the Royal Chemical Society,London, A (1991), Vol. 433, pp. 499-520). DIFFaX is the simulationprogram selected by and available from the International ZeoliteAssociation to simulate the XRD powder patterns for intergrown phases ofzeolites (see “Collection of Simulated XRD Powder Patterns for Zeolites”by M. M. J. Treacy and J. B. Higgins, 2001, Fourth Edition, published onbehalf of the Structure Commission of the International ZeoliteAssociation). It has also been used to theoretically study intergrownphases of AEI, CHA, SAV, and KFI, as reported by K. P. Lillerud et al.in “Studies in Surface Science and Catalysis”, 1994, Vol. 84, pp.543-550. DIFFaX is a well-known and established method to characterizecrystalline materials with planar faults such as the intergrownmolecular sieves of the present invention.

As the ratio of AEI increases relative to CHA in the intergrown phase,one can observe a decrease in intensity of certain peaks, for example,the peak at about 2θ=25.0 and an increase in intensity of other peaks,for example, the peak at about 2θ=17.05 and the shoulder at 2θ=21.2.Intergrown phases with AEI/CHA ratios of 50/50 and above (AEI/CHA≧1.0)show a broad feature centered at about 16.9 (2θ). Intergrown phases withAEI/CHA ratios of 40/60 and lower (AEI/CHA≦0.67) show a broad featurecentered at about 18 (2θ).

Preferably, the molecular sieves obtained by the method of the presentinvention are relatively rich in CHA framework type. Such CHA-rich SAPOsare, for example, characterized by powder XRD diffraction patternsobtained from samples after calcination and avoiding re-hydration aftercalcination, having at least the reflections in the 5 to 25 (2θ) rangeas shown in Table 1 below.

TABLE 1 2θ (CuKα) 9.3-9.6 12.7-13.0 13.8-14.0 15.9-16.1 17.7-18.118.9-19.1 20.5-20.7 23.7-24.0

The XRD diffraction patterns of CHA-rich intergrown phases of AEI/CHAmay also be characterized by the absence of peaks in the 9.8 to 12.0(2θ) range and the absence of any broad feature centered at about 16.9(2θ). A further characteristic is the presence of a peak in the 17.7 to18.1 (2θ) range. The reflection peak in the 17.7-18.1 (2θ) range has arelative intensity between 0.09 and 0.4, preferably between 0.1 and 0.35with respect to the reflection peak at 17.9 (2θ) in the diffractionpattern of SAPO-34, all diffraction patterns being normalized to theintensity value of the reflection peak in the 20.5-20.7 (2θ) range.

The metalloaluminophosphate molecular sieves made by the process of thepresent invention comprise at least one intergrown phase of molecularsieves having the AEI and CHA framework types. Preferably the CHAmolecular sieve is SAPO-34 and the AEI molecular sieve is selected fromSAPO-18, ALPO-18, or a mixture of SAPO-18 and ALPO-18. Also, themetalloaluminophosphates of the present invention advantageously have asilica to alumina molar ratio (SiO₂/Al₂O₃) ranging from 0.01 to 0.6,more preferably from 0.02 to 0.20, even more preferably from 0.03 to0.19. Most preferred metalloaluminophosphate molecular sieves have asilica to alumina molar ratio from about 0.13 to about 0.24, forexample, from about 0.15 to about 0.22, such as from about 0.17 to about0.21, such as about 0.18 or about 0.19. The silica to alumina molarratio (SiO₂/Al₂O₃) is preferably determined by chemical analysis.

The metalloaluminophosphate molecular sieves of this invention has ashredded crystal morphology by SEM. Shredded crystal morphology is asexemplified by FIG. 1.

The metalloaluminophosphate molecular sieves of this invention has atleast 90 wt. % of the metalloaluminophosphate molecular sieve having aparticle size less than 1 micron, preferably below 600 nm, morepreferably less than 300 nm. and yet more preferably less than 100 nm,most preferably less than 50 nm.

In one embodiment, the molecular sieves of the present invention areprepared by a process that comprises:

(a) combining at least one silicon source, at least one metal source, atleast one structure-directing-agent (R), at least one phosphorus source,at least one aluminum source to form a mixture having a molarcomposition according to formula (III):(n)Si:Al₂:(m)P:(x)R:(y)H₂O:(z)M  (III)wherein n is in the range of from about 0.005 to about 0.6, m is in therange of from about 1.2 to about 2.4, x is in the range of from about0.5 to about 2, y is in the range of from about 10 to about 60, and z isin the range of from about 0.001 to 1; and(b) submitting the mixture to crystallization conditions to form themetalloaluminophosphate molecular sieve.

Preferably, n is in the range of from 0.005 to 0.5. In another preferredembodiment, n is in the range of from about 0.05 to about 0.4, such asfrom about 0.1 to about 0.3. Preferably, m is in the range of from 1.2to 2.2. In another preferred embodiment, m is in the range of from about1.2 to about 2, such as from about 1.5 to about 1.8. Preferably, x is inthe range of from 0.5 to 1.5. In another preferred embodiment, x is inthe range of from about 0.5 to about 1, such as from about 0.8 to about0.9. Preferably, y is in the range of from 10 to 40. In anotherpreferred embodiment, y is in the range of from about 10 to about 30,such as from about 10 to about 20. Preferably, z is in the range of from0.01 to 0.9, more preferably z is in the range of from 0.02 to 0.9, andmost preferably z is in the range of from 0.05 to 0.9. In anotherpreferred embodiment, z is in the range of from about 0.1 to about 0.4,such as from about 0.1 to about 0.3.

In another embodiment, the molecular sieves of the present invention areprepared by a process that comprises:

(a) combining at least one silicon source, at least one metal source, atleast one structure-directing-agent (R), at least one phosphorus source,at least one aluminum source to form a mixture having a molarcomposition according to formula (IV):(n)SiO₂:Al₂O₃:(m)P₂O₅:(x)R:(y)H₂O:(z)MO₂  (IV)wherein n is in the range of from about 0.005 to about 0.6, m is in therange of from about 0.6 to about 1.2, x is in the range of from about0.5 to about 2, y is in the range of from about 10 to about 60, and z isin the range of from about 0.001 to 1; and(b) submitting the mixture to crystallization conditions to form themetalloaluminophosphate molecular sieve.

Preferably, n is in the range of from 0.005 to 0.5. In another preferredembodiment, n is in the range of from about 0.05 to about 0.4, such asfrom about 0.1 to about 0.3. Preferably, m is in the range of from 1.2to 2.2. In another preferred embodiment, m is in the range of from about1.2 to about 2, such as from about 1.5 to about 1.8. Preferably, x is inthe range of from 0.5 to 1.5. In another preferred embodiment, x is inthe range of from about 0.5 to about 1, such as from about 0.8 to about0.9. Preferably, y is in the range of from 10 to 40. In anotherpreferred embodiment, y is in the range of from about 10 to about 30,such as from about 10 to about 20. Preferably, z is in the range of from0.01 to 0.9, more preferably z is in the range of from 0.02 to 0.9, andmost preferably z is in the range of from 0.05 to 0.9. In anotherpreferred embodiment, z is in the range of from about 0.1 to about 0.4,such as from about 0.1 to about 0.3.

It will be understood that the molar ratio of silica to alumina in thereaction mixture will influence the silica to alumina ratio of themolecular sieve after synthesis.

In one embodiment, the molecular sieves of the present invention have acomposition represented by empirical formula (V) on an anhydrous basisas:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (V)wherein p is in the range of from about 0.001 to about 0.5, preferably0.001 to 0.4, more preferably from 0.001 to 0.3, most preferably from0.001 to 0.2; q, r, s, and t represent the mole fraction of M, Si, Al,and P as tetrahedral oxides, where M is a metal selected from one ofGroup IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB, and Lanthanide's ofthe Periodic Table of Elements, preferably M is selected from one of thegroup consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, andZr. In an embodiment, p is greater than or equal to 0.2, and q, r, s,and t are greater than or equal to 0.01. In another embodiment, p isgreater than 0.1 to about 1, q is greater than 0.001 to about 0.25, r isgreater than 0.01 to about 0.15, s is in the range of from 0.4 to 0.5,and t is in the range of from 0.25 to 0.5, more preferably p is from0.15 to 0.7, q is from 0.0001 to 0.1, r is from 0.01 to 0.1, s is from0.4 to 0.5, and t is from 0.3 to 0.5.

Treatment of the synthesis mixture to form the desired crystallinemolecular sieve typically takes place by hydrothermal treatment, and ispreferably carried out under autogenous pressure, for example, in anautoclave, preferably a stainless steel autoclave, optionally, teflonlined. The treatment may, for example, be carried out at a temperaturewithin the range of from 50° C., preferably from 90° C., especially 120°C. to 250° C. The treatment may, for example, be carried out for aperiod within the range of from 1 to 200 hours, preferably up to 100hours, depending on the temperature. The procedure may include an agingperiod, either at room temperature or at a moderately elevatedtemperature, before the hydrothermal treatment at more elevatedtemperatures takes place. The latter may include a period of gradual orstepwise variation in temperature.

In a preferred embodiment, the metal used is Zn and/or Mg. These metalsin the synthesis mixture are introduced as acetate, chloride, nitrate orsulfate salt, for example, zinc acetate, zinc nitrate, magnesiumacetate, and magnesium nitrate.

In a preferred embodiment, the phosphorus used phosphoric acid. Thephosphorus in the synthesis mixture is introduced as phosphoric acid,organic phosphates, e.g., triethylphosphate and aluminophosphates.

In a preferred embodiment, the aluminum used is alumina hydrate and/oralumina. The aluminum in the synthesis mixture is introduced as aluminahydrate, alumina, sodium aluminate, pseudoboehmite, organic aluminumsources, e.g., alkoxides, for example, aluminum isopropoxide andaluminum phosphate.

In a preferred embodiment, the silicon is fumed silica. The silicon inthe synthesis mixture is introduced as fumed silica, e.g., that soldunder the trade name Aerosil; an aqueous colloidal suspension of silica,e.g., that sold under the trade name Ludox AS40 or Ludox HS40; ororganic silicon sources, e.g., a tetraalkyl orthosilicate, especiallytetraethyl orthosilicate, although the invention is more especially ofimportance when the source of silicon is an inorganic source, it beingunderstood that dissolution in the basic organic solvent may effectphysical or chemical changes in the source as added.

In addition, the synthesis mixture will contain a structure-directingtemplate (hereinafter “template”), preferably an organicstructure-directing agent. In general, these compounds are organicbases, especially nitrogen-containing bases, more especially amines andquaternary ammonium compounds, used either singly or in mixtures.

The amount of organic structure-directing agent is such that the molarratio of directing agent to alumina is less than 2, preferably fromabout 0.5 to about 2, preferably from about 0.6 to about 1.5, such asfrom about 0.7 to about 1.

While not wishing to be bound by theory, we believe that the addition ofrelatively small amount of a metal (represented by M) provides a verysignificant improvement in the yield of the molecular sieve.Accordingly, this invention uses low amounts of expensivestructure-directing templates per unit alumina and surprisingly produceshigher molecular sieve yields, as illustrated in the examples below.Compared to molecular sieve synthesis processes not employing the metal(M) that use higher template to alumina molar ratios, the presentinvention provides a synthesis method that is less expensive and thatproduces higher overall yields of molecular sieve. In one embodiment,this invention has a metalloaluminophosphate molecular sieve yield atleast 0.5 wt. %, preferably 1 wt. %, higher than the yield obtained witha synthesis mixture having a template to alumina molar ratio of 1 orhigher. As shown in the examples, it is possible to secure 10 wt. % orgreater yield improvements through use of the present invention.However, it may often be desirable to use a smaller amount of the metalM than that necessary to secure the max yield improvement.

As structure-directing templates there may be mentioned, for example,tetraethyl ammonium compounds, cyclopentylamine, aminomethylcyclohexane, piperidine, dimethyl cyclohexyl amine, triethylamine,cyclohexylamine, trimethyl hydroxyethylamine, morpholine, dipropylamine(DPA), pyridine, isopropylamine, and mixtures thereof. Preferredtemplates are triethylamine, cyclohexylamine, piperidine, pyridine,isopropylamine, tetraethyl ammonium compounds, dipropylamine, andmixtures thereof. The tetraethylammonium compounds include tetraethylammonium hydroxide (TEAOH), and tetraethyl ammonium phosphate, fluoride,bromide, chloride, and acetate. Preferred tetraethyl ammonium compoundsare the hydroxide and the phosphate. The molecular sieve structure maybe effectively controlled using combinations of templates.

Thermal treatment of the molecular sieve synthesis mixture may becarried out with or without agitation, such as stirring or tumbling(rotating the vessel about a “horizontal axis”. If desired, thesynthesis mixture may be stirred or tumbled during an initial part ofthe heating stage, for example, from room temperature to an elevatedtemperature, e.g., the final treatment temperature, and be static forthe remainder of the thermo-treatment.

In one practical embodiment, the crystallization process of theinvention comprises at least two stages; namely a first stage in whichthe (silico)aluminophosphate precursor material is produced and a secondstage in which the precursor material is converted into the desiredintergrown AEI/CHA framework type molecular sieve. In the first stage,the synthesis mixture is heated under agitation to raise its temperatureat a rate of at least 8° C./hour to a first temperature of about 99° C.to about 150° C., such as about 115° C. to about 125° C. The synthesismixture is then maintained at said first temperature, preferably withthe agitation being continued, for a time, typically from about 0.5hours to about 120 hours, to form an intermediate product mixturecontaining a slurry of the precursor material. The intermediate productmixture is then heated so as to raise its temperature at a rate of atleast 8° C./hour, such as at a rate of from about 10° C./hour to about40° C./hour, to a second temperature generally from about 150° C. toabout 220° C., such as about 165° C. to about 190° C. This secondheating step can be conducted under static conditions or with reducedagitation as compared with the first heating step. The second synthesismixture is then maintained at said second temperature until theintergrown molecular sieve crystallizes from the mixture, whichgenerally takes from about 2 to about 150 hours; such as from about 5 toabout 100 hours, for example, from about 10 to about 50 hours.

The invention contemplates the use of a silicon source in the form ofthe silicon component in a solution, preferably a basic organicsolution, in the hydrothermal synthesis of a metalloaluminophosphatemolecular sieve to reduce the particle size of the product.

Typically, the molecular sieve product is formed as a slurry and can berecovered by standard means, such as by centrifugation or filtration.The separated molecular sieve product can also be washed, recovered bycentrifugation or filtration and dried, or can be stored as an aqueousslurry.

As a result of the molecular sieve crystallization process, therecovered molecular sieve contains within its pores at least a portionof the template used. The crystalline structure essentially wraps aroundthe template, and the template should be removed to obtain catalyticactivity. In a preferred embodiment, activation is performed in such amanner that the template is removed from the molecular sieve, leavingactive catalytic sites with the microporous channels of the molecularsieve open for contact with a feedstock. The activation process istypically accomplished by calcining, or essentially heating themolecular sieve comprising the template at a temperature of from 200 to800° C. in the presence of an oxygen-containing gas. In some cases, itmay be desirable to heat the molecular sieve in an environment having alow oxygen concentration. This type of process can be used for partialor complete removal of the template from the intracrystalline poresystem. In other cases, particularly with smaller templates, complete orpartial removal from the sieve can be accomplished by conventionaldesorption processes.

The metalloaluminophosphate catalyst may be pretreated underpre-treatment conditions sufficient to remove metal from framework.Inventors anticipate that the metal removed from framework may reside inthe cage of the molecular sieve which may improve both catalyticactivity and/or selectivity. While not wishing to be bound by theory,catalytic selectivity may be improved due to partial blockage of thecage by the metal removed from the framework. Also, the metal removedfrom framework metal may have higher activity than the metalincorporated by conventional method, such as, ion-exchange.

Once the molecular sieve is made, it can be formulated into a catalystby combining the molecular sieve with other materials that provideadditional hardness or catalytic activity to the finished catalystproduct. When combined with these other materials, the resultingcomposition is typically referred to as a metalloaluminophosphatecatalyst, with the catalyst comprising the molecular sieve. Thisinvention also relates to catalysts comprising the molecular sieves ofthis invention.

Materials that can be blended with the molecular sieve can be variousinert or catalytically active materials, or various binder materials.These materials include compositions such as kaolin and other clays,various forms of rare earth metals, other non-zeolite catalystcomponents, zeolite catalyst components, alumina or alumina sol,titania, zirconia, quartz, silica, or silica sol, and mixtures thereof.These components are also effective in reducing overall catalyst cost,acting as a thermal sink to assist in heat shielding the catalyst duringregeneration, densifying the catalyst and increasing catalyst strength.When blended with non-metalloaluminophosphate molecular sieve materials,the amount of molecular sieve contained in the final catalyst product isin the range of from 10 to 90 wt. % of the total catalyst, preferably 20to 70 wt. % of the total catalyst.

The metalloaluminophosphate molecular sieves synthesized in accordancewith the present method can be used to dry gases and liquids; forselective molecular separation based on size and polar properties; asion-exchangers; as catalysts in cracking, hydrocracking,disproportionation, alkylation, isomerization, and oxidation; aschemical carriers; in gas chromatography; and in the petroleum industryto remove normal paraffins from distillates.

The metalloaluminophosphate molecular sieves of the present inventionare particularly suited for the catalytic conversion of oxygenates tohydrocarbons. Accordingly, the present invention also relates to amethod for making an olefin product from an oxygenate feedstock whereinthe oxygenate feedstock is contacted with the catalyst of this inventioncomprising the molecular sieve of this invention under conditionseffective to convert the oxygenate feedstock to olefin products. Whencompared to other metalloaluminophosphates under the same operatingconditions, the metalloaluminophosphates of the present inventionexhibit higher selectivity to light olefins, and produce fewerby-products.

In this process a feedstock containing an oxygenate contacts a catalystcomprising the molecular sieve in a reaction zone of a reactor atconditions effective to produce light olefins, particularly ethylene andpropylene. Typically, the oxygenate feedstock is contacted with thecatalyst containing the molecular sieve when the oxygenate is in vaporphase. Alternately, the process may be carried out in a liquid or amixed vapor/liquid phase. When the process is carried out in a liquidphase or a mixed vapor/liquid phase, different conversions andselectivities of feed-to-product may result depending upon the catalystand reaction conditions.

In this oxygenate conversion process, olefins can generally be producedat a wide range of temperatures. An effective operating temperaturerange can be from about 200° C. to 700° C. At the lower end of thetemperature range, the formation of the desired olefin products maybecome markedly slow. At the upper end of the temperature range, theprocess may not form an optimum amount of product. An operatingtemperature of at least 300° C., and up to 525° C. is preferred.

In a preferred embodiment, it is highly desirable to operate at atemperature of at least 300° C. and a Temperature Corrected NormalizedMethane Sensitivity (TCNMS) of less than about 0.016, preferably lessthan about 0.012, more preferably less than about 0.01. It isparticularly preferred that the reaction conditions for making olefinfrom oxygenate comprise a WHSV of at least about 20 hr⁻¹ producingolefins and a TCNMS of less than about 0.016.

As used herein, TCNMS is defined as the Normalized Methane Selectivity(NMS) when the temperature is less than 400° C. The NMS is defined asthe methane product yield divided by the ethylene product yield whereineach yield is measured on, or is converted to, a weight % basis. Whenthe temperature is 400° C. or greater, the TCNMS is defined by thefollowing equation, in which T is the average temperature within thereactor in ° C.:

${TCNMS} = \frac{NMS}{1 + ( {( {( {T - 400} )/400} ) \times 14.84} )}$

The pressure also may vary over a wide range, including autogenouspressures. Preferred pressures are in the range of about 5 kpa-a toabout 5 MPa-a, with the most preferred range being of from about 50kPa-a to about 0.5 MPa-a. The foregoing pressures are exclusive of anyoxygen depleted diluent, and thus, refer to the partial pressure of theoxygenates and/or mixtures thereof with feedstock.

The process can be carried out in a dynamic bed system or any systemusing a variety of transport beds, although a fixed-bed system could beused. It is particularly desirable to operate the reaction process athigh space velocities.

The process may be carried out in a batch, semi-continuous, orcontinuous fashion. The process can be conducted in a single reactionzone or a number of reaction zones arranged in series or in parallel.

The conversion of oxygenates to produce olefins is preferably carriedout in a large-scale continuous catalytic reactor. This type of reactorincludes fluid-bed reactors and concurrent riser reactors as describedin “Free Fall Reactor,” Fluidization Engineering, D. Kunii and O.Levenspiel, Robert E. Krieger Publishing Co. NY, 1977, incorporated inits entirety herein by reference. Additionally, countercurrent free fallreactors may be used in the conversion process. See, for example, U.S.Pat. No. 4,068,136 and “Riser Reactor”, Fluidization and Fluid-ParticleSystems, pp. 48-59, F. A. Zenz and D. F. Othmo, Reinhold PublishingCorp., NY, 1960, the descriptions of which are expressly incorporatedherein by reference.

Any standard commercial scale reactor system can be used, for example,fixed-bed or moving bed systems. The commercial scale reactor systemscan be operated at a weight hourly space velocity (WHSV) of from 1 hr⁻¹to 1000 hr⁻¹. In the case of commercial scale reactors, WHSV is definedas the weight of hydrocarbon in the feedstock per hour per weight ofmetalloaluminophosphate molecular sieve content of the catalyst. Thehydrocarbon content is the oxygenate content and the content of anyhydrocarbon which may be present with the oxygenate. Themetalloaluminophosphate molecular sieve content means only themetalloaluminophosphate molecular sieve portion that is contained withinthe catalyst. This excludes components such as binders, diluents,inerts, rare earth components, etc.

One or more inert diluents may be present in the feedstock, for example,in an amount of from 1 to 95 mol. %, based on the total number of molesof all feed and diluent components fed to the reaction zone. Typicaldiluents include, but are not necessarily limited to helium, argon,nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins,alkanes (especially methane, ethane, and propane), alkylenes, aromaticcompounds, and mixtures thereof. The preferred diluents are water andnitrogen. Water can be injected in either liquid or vapor form.

The level of conversion of the oxygenates is maintained to reduce thelevel of unwanted by-products. Conversion is also maintainedsufficiently high to avoid the need for commercially undesirable levelsof recycling of unreacted feeds. A reduction in unwanted by-products isseen when conversion moves from 100 mol. % to about 98 mol. % or less.Recycling up to as much as about 50 mol. % of the feed is preferred.Therefore, conversions levels which achieve both goals are from about 50mol. % to about 98 mol. % and, desirably, from about 85 mol. % to about98 mol. %. However, it is also acceptable to achieve conversion between98 mol. % and 100 mol. % in order to simplify the recycling process.Oxygenate conversion is maintained using a number of methods familiar topersons of ordinary skill in the art. Examples include, but are notnecessarily limited to, adjusting one or more of the following: thereaction temperature; pressure; flow rate (i.e., WHSV); level and degreeof catalyst regeneration; amount of catalyst re-circulation; thespecific reactor configuration; the feed composition; and otherparameters which affect the conversion.

If regeneration is used, the molecular sieve catalyst can becontinuously introduced as a moving bed to a regeneration zone where itis regenerated, such as, for example, by removing carbonaceous materialsor by oxidation in an oxygen-containing atmosphere. In a preferredembodiment, the catalyst is subject to a regeneration step by burningoff carbonaceous deposits accumulated during the conversion reactions.

The oxygenate feedstock comprises at least one organic compound whichcontains at least one oxygen atom, such as aliphatic alcohols, ethers,carbonyl compounds (aldehydes, ketones, carboxylic acids, carbonates,esters and the like). When the oxygenate is an alcohol, the alcohol caninclude an aliphatic moiety having from 1 to 10 carbon atoms, morepreferably from 1 to 4 carbon atoms. Representative alcohols include,but are not necessarily limited to lower straight and branched chainaliphatic alcohols and their unsaturated counterparts. Examples ofsuitable oxygenates include, but are not limited to: methanol; ethanol;n-propanol; isopropanol; C₄-C₂₀ alcohols; methyl ethyl ether; dimethylether; diethyl ether; di-isopropyl ether; formaldehyde; dimethylcarbonate; dimethyl ketone; acetic acid; and mixtures thereof. Preferredoxygenates are methanol, dimethyl ether, or a mixture thereof. The mostpreferred oxygenate compound is methanol.

The process for making an olefin product from an oxygenate feedstock bycontacting the oxygenate feedstock with a catalyst comprising ametalloaluminophosphate of the present invention has good catalyticperformance. This is reflected by a selectivity to ethylene andpropylene equal to or greater than 75.0%, and/or an ethylene topropylene ratio equal to or greater than 0.75 and/or a selectivity topropane equal to or lower than 1.0%.

The method of making the olefin products from an oxygenate feedstock caninclude the additional step of making the oxygenate feedstock fromhydrocarbons such as oil, coal, tar sand, shale, biomass, and naturalgas. Methods for making oxygenate feedstocks are known in the art. Thesemethods include fermentation to alcohol or ether, making synthesis gas,then converting the synthesis gas to alcohol or ether. Synthesis gas canbe produced by known processes such as steam reforming, autothermalreforming, and partial oxidization.

One skilled in the art will also appreciate that the olefin productsmade by the oxygenate-to-olefin conversion reaction using the molecularsieve of the present invention can be polymerized to form polyolefins,particularly polyethylenes and polypropylenes. Processes for formingpolyolefins from olefins are known in the art. Catalytic processes arepreferred. Particularly preferred are metallocene, Ziegler/Natta andacid catalytic systems. See, for example, U.S. Pat. Nos. 3,258,455;3,305,538; 3,364,190; 5,892,079; 4,659,685; 4,076,698; 3,645,992;4,302,565; and 4,243,691, the catalyst and process descriptions of eachbeing expressly incorporated herein by reference. In general, thesemethods involve contacting the olefin product with a polyolefin-formingcatalyst at a pressure and temperature effective to form the polyolefinproduct.

In addition to polyolefins, numerous other olefin derivatives may beformed from the olefins recovered from this invention. These include,but are not limited to, aldehydes, alcohols, acetic acid, linear alphaolefins, vinyl acetate, ethylene dichloride and vinyl chloride,ethylbenzene, ethylene oxide, cumene, isopropyl alcohol, acrolein, allylchloride, propylene oxide, acrylic acid, ethylene-propylene rubbers, andacrylonitrile, and trimers and dimers of ethylene, propylene orbutylenes. The methods of manufacturing these derivatives are well knownin the art, and therefore, are not discussed herein.

Another particular use of the composite material of the invention is inthe reaction of organic oxygenates with ammonia to producemonoalkylamines and dialkylamines, particularly methylamine anddimethylamine. Examples of suitable organic oxygenate compounds for usein this reaction include alcohols having 1 to 3 carbon atoms,specifically, methanol, ethanol, n-propanol and isopropanol, and theirether counterparts, including methyl ethyl ether, dimethyl ether,diethyl ether and di-isopropyl ether. The reaction is conducted,preferably, but not exclusively, in a flowing system in a gaseous fixedbed or fluidized bed, with the molar ratio of ammonia to oxygenate beinggenerally from about 0.5 to about 20, such as about 1 to about 5. Thereaction conditions typically include a temperature of about 200 to 400°C., such as about 250 to about 360° C., a pressure of about 0.1 to about10 MPa, such as about 0.5 to about 2 MPa and gas hourly space velocity,GHSV, of about 100 to about 10,000 hr⁻¹.

EXAMPLES

The following Examples, in which parts are by weight unless otherwiseindicated, illustrate preferred embodiments of the invention. The sourceand purity of starting materials are those first given, unless indicatedotherwise.

Yield is calculated by dividing the weight of the product (washed anddried overnight at 120° C.) by the initial weight of the gel asfollowing:

${Yield} = {\frac{{Product}\mspace{14mu}{dry}\mspace{14mu}{weight}\mspace{14mu}(g)}{{Initial}\mspace{14mu}{gel}\mspace{14mu}{weight}\mspace{14mu}(g)}{\%.}}$

SEM was obtained on a JEOL JSM-6340F Field Emission Scanning ElectronMicroscope, using a magnification of 20,000 times at a voltage of 2 keV.

In these examples, the XRD diffraction patterns were recorded on aSCINTAG X2 X-Ray Powder Diffractometer (Scintag Inc. USA), using copperKα radiation. The molecular sieve samples were calcined afterpreparation and kept moisture-free according to the following procedure:

About 2 grams of molecular sieve were heated-up from room temperature to200° C. under a flow of nitrogen at a rate of 2° C. per minute. Thetemperature was held at 200° C. for 30 minutes. Then the sample washeated-up from 200° C. to 650° C. under nitrogen at a rate of 2° C. perminute. The sample was held at 650° C. under nitrogen for 5 hours.Nitrogen was then replaced by air and the sample was kept at 650° C.under air for 3 hours. The sample was then cooled to 200° C. and kept at200° C. to prevent hydration. The hot sample was then transferred intothe XRD sample cup and was covered by Mylar foil to prevent hydration.XRD diffraction patterns were recorded in the 20 range of 12 to 24degrees.

In these examples, DIFFaX analysis was used to determine the AEI/CHAratio of the molecular sieves. For the purpose of this application, theDIFFaX analysis was performed as disclosed in U.S. Pat. No. 6,812,372,fully incorporated herein by reference. If the molecular sieve containedmore than one AEI/CHA intergrown phase, DIFFaX analysis was performed asdisclosed in U.S. patent application Ser. No. 11/072,830.

Comparative Example

A synthesis mixture with the following molar ratios (VI) was preparedwith the quantities indicated in the table:0.29SiO₂:Al₂O₃:P₂O₅:TEAOH: 1.58DPA:52H₂O  (VI)by adding Ludox AS40 (SiO₂ 40 wt. % in water) to a mixture of phosphoricacid, water and Condea Pural SB (Al₂O₃ pseudoboehmite containing 25 wt.% of water). TEAOH (Eastern Chemical) was added to the mixture andfollowed by DPA (Eastern Chemical). The homogeneous slurry was heated ina stainless steel autoclave to 175° C. in 2 hours and kept at thistemperature for 60 hrs. After cooling the product was washed and driedovernight at 120° C. The yield calculated by dividing the weight of thedried product by the initial weight of the gel was 11.1%. According toXRD, the product was having the CHA framework type structure with aparticle size ranging between 0.5 and 20 microns as measured by SEM. Thesolid product has a Si/Al₂ ratio of 0.33 measured by chemical analysis.

Example 1

A synthesis mixture with the following molar ratios (VII) was preparedwith the quantities indicated in Table 2:0.05SiO₂:Al₂O₃:P₂O₅:TEAOH:35H₂O:0.025MgO  (VII)by adding Ludox AS40 (SiO₂ 40 wt. % in water) to a diluted solution ofphosphoric acid and TEAOH (Eastern Chemical). The Magnesium acetatetetrahydrate (Fluka p.a. >99.5%) was added. The Condea Pural SB (Al₂O₃pseudoboehmite containing 25 wt. % of water) was added to this mixture.The homogeneous slurry was heated in a stainless steel autoclave to 175°C. with a heating rate of 20° C./hr and kept at this temperature for 56hrs. Tumbling (60 rpm) was applied during the whole hydrothermaltreatment. After cooling the product was washed and dried overnight at120° C. The yield calculated by dividing the weight of the dried productby the initial weight of the gel was 20.6%. According to XRD, theproduct was an intergrown phase of molecular sieves having AEI and CHAframework types, with a particle size of less than 0.5 micron asmeasured by SEM. The solid product has a AEI/CHA ratio of 20/80 asdetermined by DIFFaX. The solid product has a Si/Al₂ ratio of 0.06 andMg/Al₂ ratio of 0.04 measured by chemical analysis. The FWHM of the XRDpeak around 20.6 degree (2θ) is greater than 0.1 degree (2θ).

TABLE 2 Proportion (Comparative Proportion Proportion ProportionProportion Proportion Component Example) (Example 1) (Example 2)(Example 3) (Example 4) (Example 5) Colloidal silica 22.5 0.89 0.98 0.991 1.8 (Ludox AS40) 40 wt. % in water TEAOH, (Eastern 183.31 51.19 51.1150.94 50.4 50.7 Chemical) 35 wt. % in water DPA 80.79 0 0 0 0 0(Dipropylamine, Eastern Chemical MgAc₂, (Aldrich 0 0.66 1.3 2.6 5.125.15 Co.), 99.5 wt. % Al₂O₃ (Condea 68.06 16.6 16.47 16.35 14.67 14.67Pural SB) H₃PO₄ (Acros), 115.74 28.21 28.06 27.86 27.86 27.58 85 wt. %in water Water 284.71 28.11 27.26 26.5 26.19 25.64 Yield (%) 11.1 20.621.8 22.7 24.3 25.2

Example 2

A synthesis mixture with the following molar ratios (VIII) was preparedas described in Example 1 with the quantities indicated in Table 2:0.05SiO₂:Al₂O₃:P₂O₅:TEAOH:35H₂O:0.05MgO  (VIII)

The homogeneous slurry was heated in a stainless steel autoclave to 175°C. with a heating rate of 20° C./hr and kept at this temperature for 48hrs. Tumbling (60 rpm) was applied during the whole hydrothermaltreatment. After cooling the product was washed and dried overnight at120° C. The yield calculated by dividing the weight of the dried productby the initial weight of the gel was 21.8%. According to XRD, theproduct was an intergrown phase of molecular sieves having AEI and CHAframework types, with a particle size of less than 1.0 micron asmeasured by SEM. The solid product has a AEI/CHA ratio of 20/80 asdetermined by DIFFaX. The solid product has a Si/Al₂ ratio of 0.07 andMg/Al₂ ratio of 0.03 measured by chemical analysis. The FWHM of the XRDpeak around 20.6 degree (2θ) is greater than 0.1 degree (2θ).

Example 3

A synthesis mixture with the following molar ratios (IX) was prepared asdescribed in Example 1 with the quantities indicated in Table 2:0.05SiO₂:Al₂O₃:P₂O₅:TEAOH:35H₂O:0.1MgO  (IX)

The homogeneous slurry was heated in a stainless steel autoclave to 175°C. with a heating rate of 20° C./hr and kept at this temperature for 48hrs. Tumbling (60 rpm) was applied during the whole hydrothermaltreatment. After cooling the product was washed and dried overnight at120° C. The yield calculated by dividing the weight of the dried productby the initial weight of the gel was 22.7%. According to XRD, theproduct has CHA framework type and is substantially free of non-CHAframework type molecular sieve, with a particle size of less than 0.3micron as measured by SEM. The solid product has a Si/Al₂ ratio of 0.06and Mg/Al₂ ratio of 0.12 measured by chemical analysis. The FWHM of theXRD peak around 20.6 degree (2θ) is greater than 0.1 degree (2θ).

Example 4

A synthesis mixture with the following molar ratios (X) was prepared asdescribed in Example 1 with the quantities indicated in Table 2:0.05SiO₂:0.9Al₂O₃:P₂O₅:TEAOH:35H₂O:0.2MgO  (X)

The homogeneous slurry was heated in a stainless steel autoclave to 175°C. with a heating rate of 20° C./hr and kept at this temperature for 48hrs. Tumbling (60 rpm) was applied during the whole hydrothermaltreatment. After cooling the product was washed and dried overnight at120° C. The yield calculated by dividing the weight of the dried productby the initial weight of the gel was 24.3%. According to XRD, theproduct has CHA framework type and is substantially free of non-CHAframework type molecular sieve. The SEM shows fragmented particles. Thesolid product has a Si/Al₂ ratio of 0.06 and Mg/Al₂ ratio of 0.22measured by chemical analysis. The FWHM of the XRD peak around 20.6degree (2θ) is greater than 0.1 degree (2θ).

Example 5

A synthesis mixture with the following molar ratios (XI) was prepared asdescribed in Example 1 with the quantities indicated in Table 2:0.05SiO₂:0.9Al₂O₃:P₂O₅:TEAOH:35H₂O:0.02MgO  (XI)

The homogeneous slurry was heated in a stainless steel autoclave to 175°C. with a heating rate of 20° C./hr and kept at this temperature for 48hrs. Tumbling (60 rpm) was applied during the whole hydrothermaltreatment. After cooling the product was washed and dried overnight at120° C. The yield calculated by dividing the weight of the dried productby the initial weight of the gel was 25.2%. According to XRD, theproduct was an intergrown phase of molecular sieves having AEI and CHAframework types. The SEM shows fragmented particles. The solid producthas a AEI/CHA ratio of 10/90 as determined by DIFFaX. The solid producthas a Si/Al₂ ratio of 0.10 and Mg/Al₂ ratio of 0.25 measured by chemicalanalysis. The FWHM of the XRD peak around 20.6 degree (2θ) is greaterthan 0.1 degree (2θ).

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

1. A process for manufacturing a metalloaluminophosphate molecularsieve, said process comprising the steps of: (a) combining at least onesilicon source, at least one metal source, at least onestructure-directing-agent (R), at least one phosphorus source, and atleast one aluminum source to form a mixture having a molar compositionaccording to formula (XII):(n)Si:Al₂:(m)P:(x)R:(y)H₂O:(z)M  (XII) wherein n is in the range of fromabout 0.005 to about 0.6, m is in the range of from about 1.2 to about2.4, x is in the range of from about 0.5 to about 2, y is in the rangeof from about 10 to about 60, and z is in the range of from about 0.001to 1; and (b) submitting said mixture to crystallization conditions toform said metalloaluminophosphate molecular sieve, wherein saidmetalloaluminophosphate molecular sieve has an X-ray diffraction patternhaving a FWHM greater than 0.10 degree (2θ) and an AEI/CHA frameworktype ratio of from about 0/100 to about 40/60 as determined by DIFFaXanalysis.
 2. The process of claim 1, wherein said step (b) furthercomprises an agitation step.
 3. The process of claim 1, wherein saidcrystallization conditions comprise a temperature range between about100° C. and about 250° C.
 4. The process of claim 1, wherein said metalsource comprises at least one of magnesium compounds, zinc compounds, orany combination thereof.
 5. The process of claim 1, wherein saidstructure-directing-agent comprises at least one of tetraethylammoniumhydroxide, tetraethylammonium phosphate, tetraethylammonium fluoride,tetraethylammonium bromide, tetraethylammonium chloride,tetraethylammonium acetate, cyclopentylamine, aminomethyl cyclohexane,piperidine, dimethyl cyclohexyl amine, triethylamine, cyclohexylamine,trimethyl hydroxyethylamine, morpholine, dipropylamine (DPA), pyridine,isopropylamine, or any combination thereof.
 6. The process of claim 1,wherein said structure-directing-agent comprises tetraethylammoniumhydroxide.
 7. The process of claim 1, wherein saidmetalloaluminophosphate molecular sieve has a composition represented byempirical formula (XIII) on an anhydrous basis as:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (XIII) wherein p is in the range of fromabout 0.001 to about 0.5, q is in the range of from about 0.001 to about0.25, r is in the range of from about 0.01 to about 0.15, s is in therange of from about 0.01 to about 0.6, t is in the range of from about0.01 to 0.6, and the sum of q, r, s, and t is
 1. 8. The process of claim7, wherein said q is in the range of from about 0.01 to about 0.25. 9.The process of claim 7, wherein said metalloaluminophosphate molecularsieve has a shredded crystal morphology by SEM.
 10. The process of claim7, wherein, after calcination, said metalloaluminophosphate molecularsieve has an X-ray diffraction pattern having a FWHM greater than 0.15degree (2θ).
 11. The process of claim 1, wherein said silicon sourcecomprises an inorganic silicon compound.
 12. The process of claim 11,wherein said inorganic silicon compound is a colloidal silica.
 13. Theprocess of claim 1, wherein at least 90 wt. % of saidmetalloaluminophosphate molecular sieve has a particle size less than100 nm.
 14. The process of claim 1, wherein said metalloaluminophosphatemolecular sieve is substantially free of non-CHA framework type.
 15. Theprocess of claim 14, wherein at least 90 wt. % of saidmetalloaluminophosphate molecular sieve has a particle size less than100 nm.
 16. The process of claim 14, wherein, after calcination, saidmetalloaluminophosphate molecular sieve has an X-ray diffraction patternhaving a FWHM greater than 0.15 degree (2θ).
 17. The process of claim 1,wherein said metalloaluminophosphate molecular sieve has an AEI/CHAratio of from about 7/93 to 38/62.
 18. The process of claim 17, wherein,after calcination, said metalloaluminophosphate molecular sieve has anX-ray diffraction pattern having at least one reflection peak in each ofthe following ranges in the 5 to 25 (2θ) range: 2θ (CuKα) 9.3-9.612.7-13.0 13.8-14.0 15.9-16.1 17.7-18.1 18.9-19.1 20.5-20.7  23.7-24.0.


19. The process of claim 18, wherein said X-ray diffraction pattern hasno reflection peak in the 9.8 to 12.0 (2θ) range.
 20. The process ofclaim 18, wherein said X-ray diffraction pattern has no broad featurecentered at about 16.9 (2θ).
 21. The process of claim 1, wherein saidmetalloaluminophosphate molecular sieve has a shredded crystalmorphology by SEM.
 22. The process of claim 1, wherein saidmetalloaluminophosphate molecular sieve has a silica to alumina molarratio (SiO₂/Al₂O₃) ranging from 0.03 to 0.19.
 23. Ametalloaluminophosphate molecular sieve manufactured by a processcomprising the steps of: (a) combining at least one silicon source, atleast one metal source, at least one structure-directing-agent (R), atleast one phosphorus source, at least one aluminum source to form amixture having a molar composition according to formula (XIV):(n)Si:Al₂:(m)P:(x)R:(y)H₂O:(z)M  (XIV) wherein n is in the range of fromabout 0.005 to about 0.6, m is in the range of from about 1.2 to about2.4, x is in the range of from about 0.5 to about 2, y is in the rangeof from about 10 to about 60, and z is in the range of from about 0.001to 1; and (b) submitting said mixture to crystallization conditions toform said metalloaluminophosphate molecular sieve, wherein saidmetalloaluminophosphate molecular sieve has an X-ray diffraction patternhaving a FWHM greater than 0.10 degree (2θ) and an AEI/CHA frameworktype ratio of from about 0/100 to about 40/60 as determined by DIFFaXanalysis.
 24. The metalloaluminophosphate molecular sieve of claim 23,wherein at least 90 wt. % said metalloaluminophosphate molecular sievehas a particle size less than 100 nm.
 25. The metalloaluminophosphatemolecular sieve of claim 23, wherein said step (b) further comprises anagitation step.
 26. The metalloaluminophosphate molecular sieve of claim23, wherein said crystallization conditions comprise a temperature rangebetween about 100° C. and about 250° C.
 27. The metalloaluminophosphatemolecular sieve of claim 23, wherein said metal source comprises atleast one of magnesium compounds, zinc compounds, or any combinationthereof.
 28. The metalloaluminophosphate molecular sieve of claim 23,wherein said structure-directing-agent comprises at least onetetraethylammonium hydroxide, tetraethylammonium phosphate,tetraethylammonium fluoride, tetraethylammonium bromide,tetraethylammonium chloride, tetraethylammonium acetate,cyclopentylamine, aminomethyl cyclohexane, piperidine, dimethylcyclohexyl amine, triethylamine, cyclohexylamine, trimethylhydroxyethylamine, morpholine, dipropylamine (DPA), pyridine,isopropylamine, or any combination thereof.
 29. Themetalloaluminophosphate molecular sieve of claim 23, wherein saidstructure-directing-agent comprises tetraethylammonium hydroxide. 30.The metalloaluminophosphate molecular sieve of claim 23 has acomposition represented by empirical formula (XV) on an anhydrous basisas:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (XV) wherein p is in the range of fromabout 0.001 to about 0.5, q is in the range of from about 0.001 to about0.25, r is in the range of from about 0.01 to about 0.15, s is in therange of from about 0.01 to about 0.6, t is in the range of from about0.01 to 0.6, and the sum of q, r, s, and t is
 1. 31. Themetalloaluminophosphate molecular sieve of claim 30, after calcination,has an X-ray diffraction pattern having a FWHM greater than 0.15 degree(2θ).
 32. The metalloaluminophosphate molecular sieve of claim 30 havinga shredded crystal morphology by SEM.
 33. The metalloaluminophosphatemolecular sieve of claim 23, wherein said silicon source comprises aninorganic silicon compound.
 34. The metalloaluminophosphate molecularsieve of claim 33, wherein said inorganic silicon compound is acolloidal silica.
 35. The metalloaluminophosphate molecular sieve ofclaim 23, wherein said metalloaluminophosphate molecular sieve hassubstantially free of non-CHA framework type.
 36. Themetalloaluminophosphate molecular sieve of claim 35, wherein at least 90wt. % said metalloaluminophosphate molecular sieve has a particle sizeless than 100 nm.
 37. The metalloaluminophosphate molecular sieve ofclaim 23, wherein said metalloaluminophosphate molecular sieve has anAEI/CHA ratio of from about 7/93 to 38/62.
 38. Themetalloaluminophosphate molecular sieve of claim 37, after calcination,wherein said metalloaluminophosphate molecular sieve has an X-raydiffraction pattern having at least one reflection peak in each of thefollowing ranges in the 5 to 25 (2θ) range: 2θ (CuKα) 9.3-9.6 12.7-13.013.8-14.0 15.9-16.1 17.7-18.1 18.9-19.1 20.5-20.7  23.7-24.0.


39. The metalloaluminophosphate molecular sieve of claim 38, whereinsaid X-ray diffraction pattern has no reflection peak in the 9.8 to 12.0(2θ) range.
 40. The metalloaluminophosphate molecular sieve of claim 38,wherein said X-ray diffraction pattern has no broad feature centered atabout 16.9 (2θ).
 41. The metalloaluminophosphate molecular sieve ofclaim 23, after calcination, wherein said metalloaluminophosphatemolecular sieve has an X-ray diffraction pattern having a FWHM greaterthan 0.15 degree (2θ).
 42. The metalloaluminophosphate molecular sieveof claim 23, wherein said metalloaluminophosphate molecular sieve has asilica to alumina molar ratio (SiO₂/Al₂O₃) ranging from 0.02 to 0.20.43. A metalloaluminophosphate molecular sieve, saidmetalloaluminophosphate molecular sieve having a composition representedby empirical formula (XVI) on an anhydrous basis as:pR●(M_(q)Si_(r)Al_(s)P_(t))O₂  (XVI) wherein p is in the range of fromabout 0.001 to about 0.5, q is in the range of from about 0.001 to about0.25, r is in the range of from about 0.01 to about 0.15, s is in therange of from about 0.01 to about 0.6, t is in the range of from about0.01 to 0.6, and the sum of q, x, y, and z is 1, wherein saidmetalloaluminophosphate molecular sieve has an X-ray diffraction patternhaving a FWHM greater than 0.10 degree (2θ) and an AEI/CHA frameworktype ratio of from about 0/100 to about 40/60 as determined by DIFFaXanalysis.
 44. The metalloaluminophosphate molecular sieve of claim 43,wherein at least 90 wt. % said metalloaluminophosphate molecular sievehas a particle size less than 100 nm.
 45. The metalloaluminophosphatemolecular sieve of claim 43, after calcination, wherein saidmetalloaluminophosphate molecular sieve has an X-ray diffraction patternhaving a FWHM greater than 0.15 degree (2θ).
 46. Themetalloaluminophosphate molecular sieve of claim 43, after calcination,wherein said metalloaluminophosphate molecular sieve has substantiallyfree of non-CHA framework type.
 47. The metalloaluminophosphatemolecular sieve of claim 46, wherein at least 90 wt. % saidmetalloaluminophosphate molecular sieve has a particle size less than100 nm.
 48. The metalloaluminophosphate molecular sieve of claim 43,after calcination, wherein said metalloaluminophosphate molecular sievehas an AEI/CHA ratio of from about 7/93 to 38/62.
 49. Themetalloaluminophosphate molecular sieve of claim 48, wherein saidmetalloaluminophosphate molecular sieve has a shredded crystalmorphology by SEM.
 50. The metalloaluminophosphate molecular sieve ofclaim 48, after calcination, wherein said metalloaluminophosphatemolecular sieve has an X-ray diffraction pattern having a FWHM greaterthan 0.15 degree (2θ).
 51. The metalloaluminophosphate molecular sieveof claim 48, after calcination, wherein said metalloaluminophosphatemolecular sieve has an X-ray diffraction pattern having at least onereflection peak in each of the following ranges in the 5 to 25 (2θ)range: 2θ (CuKα) 9.3-9.6 12.7-13.0 13.8-14.0 15.9-16.1 17.7-18.118.9-19.1 20.5-20.7  23.7-24.0.


52. The metalloaluminophosphate molecular sieve of claim 51, whereinsaid X-ray diffraction pattern has no reflection peak in the 9.8 to 12.0(2θ) range.
 53. The metalloaluminophosphate molecular sieve of claim 51,wherein said X-ray diffraction pattern has no broad feature centered atabout 16.9 (2θ).
 54. The metalloaluminophosphate molecular sieve ofclaim 43, after calcination, wherein said metalloaluminophosphatemolecular sieve has a silica to alumina molar ratio (SiO₂/Al₂O₃) rangingfrom 0.02 to 0.20.
 55. A process for the conversion of an oxygenate toolefins, the process comprising the steps of: (i) contacting theoxygenate under catalytic conversion conditions with themetalloaluminophosphate molecular sieve made by a process comprising thesteps of: (a) combining at least one silicon source, at least one metalsource, at least one structure-directing-agent (R), at least onephosphorus source, at least one aluminum source to form a mixture havinga molar composition according to formula (XVII):(n)Si:Al₂:(m)P:(x)R:(z)M  (XVII) wherein n is in the range of from about0.005 to about 0.6, m is in the range of from about 1.2 to about 2.4, xis in the range of from about 0.5 to about 2, and z is in the range offrom about 0.001 to 1; and (b) submitting said mixture tocrystallization conditions to form said metalloaluminophosphatemolecular sieve, wherein said metalloaluminophosphate molecular sievehas an X-ray diffraction pattern having a FWHM greater than 0.10 degree(2θ) and an AEI/CHA framework type ratio of from about 0/100 to about40/60 as determined by DIFFaX analysis; and (ii) withdrawing theolefins.
 56. The process of claim 55, wherein said oxygenate comprisesat least one of methanol, ethanol, n-propanol, isopropanol, C₄-C₂₀alcohols, methyl ethyl ether, dimethyl ether, diethyl ether,di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone,acetic acid, or any combination thereof.
 57. The process of claim 55,wherein said oxygenate is methanol.
 58. A process for the conversion ofan oxygenate to alkylamines, the process comprising the steps of: (i)contacting the oxygenate with ammonia under catalytic conversionconditions with the metalloaluminophosphate molecular sieve made by aprocess comprising the steps of: (a) combining at least one siliconsource, at least one metal source, at least onestructure-directing-agent (R), at least one phosphorus source, at leastone aluminum source to form a mixture having a molar compositionaccording to formula (XVIII):(n)Si:Al₂:(m)P:(x)R:(z)M  (XVIII) wherein n is in the range of fromabout 0.005 to about 0.6, m is in the range of from about 1.2 to about2.4, x is in the range of from about 0.5 to about 2, and z is in therange of from about 0.001 to 1; and (b) submitting said mixture tocrystallization conditions to form said metalloaluminophosphatemolecular sieve, wherein said metalloaluminophosphate molecular sievehas an X-ray diffraction pattern having a FWHM greater than 0.10 degree(2θ) and an AEI/CHA framework type ratio of from about 0/100 to about40/60 as determined by DIFFaX analysis; and (ii) withdrawing thealkylamines.
 59. The process of claim 58, wherein said oxygenate ismethanol.